Additive formulation for reduction or prevention of microbially induced corrosion in concrete or cementitious material

ABSTRACT

A formulation including a material that is in a wet-state in which the material is an uncured concrete, an uncured cementitious material, or a combination thereof, a Quat Silane that cures on and/or within the material, a fungicide, and a defoamer.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation application which claims priorityfrom U.S. patent application Ser. No. 16/014,559, filed on Jun. 21,2018, which application claims priority from U.S. provisional patentapplication No. 62/524,168, filed on Jun. 23, 2017, in the United StatesPatent and Trademark Office. The disclosure of which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

The invention relates to the field of additive formulations, moreparticularly to an additive formulation used to reduce or to preventmicrobially induced corrosion in concrete, in cementitious material, ora combination thereof.

BACKGROUND OF THE INVENTION

Microbially Induced Corrosion in Concrete (MICC) is an immense problemthat causes premature failure of concrete structures that are exposedconstantly to sewage and similar corrosive environments. Prematurefailure and the need for replacement is extremely costly since in suchinfrastructure projects, the majority of cost is not the materials(concrete) but in the construction project (labor, digging, equipment,etc.). Premature failure is also unbudgeted by municipal authorities andis therefore undesired. In some cases, failure can have seriousenvironmental, safety, and infrastructural impact. For example, afailure of a sewage pipe can leach toxic contents into groundwater, orcause sink holes or other water pathways that can compromise buildingstructures in the vicinity.

MICC is an issue particularly prevalent in concrete sewer pipes, wheresulfur-loving bacteria convert gaseous H₂S into sulfuric acid, whicherodes the concrete pipes above the water line. Quat silanes (QS) (alsocommonly referred to as Silyl Quats or 1-Octadecanaminium,N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-, chloride) have beenproposed in the industry to prevent, through antimicrobial action, thebacteria from thriving, thereby reducing or eliminating the sulfuricacid attack on the concrete. Some examples of quat silanes are MicrobanAEM5772, which is 72% active, and Microban AEM 5772-5 which is 3.6%active. There is preference for QS due to its compatibility withaggregates due to its silyl groups. However, currently availableformulations of the quat silane are dilute in nature and make no attemptto negate the serious side effects that this chemical has on the curingand final physical properties of the concrete structures. In addition,dilute aqueous QS formulations have a short shelf-life due to hydrolyticinstability.

Several academic papers have examined more closely the flora involved inMICC and, while many theories abound, most have determined that theThiobacillus genus of bacteria are not the sole actors; there are fungi,particularly of the Fusarium genus, which are also present and seem toparticipate symbiotically with the bacterial species during thedeterioration process. While QS in liquid state (such as in a solutionor a suspension) has strong antifungal efficacy against a wide varietyof fungal species, it selectively losses its efficacy against fungalspecies once in its “dry film” form (i.e. once the concrete has cured)while still maintaining good antibacterial efficacy. Thus, there is aneed for truly effective and comprehensive protection of the concretestructure against MICC. Moreover, the complex interplay betweenbacterial and fungal species changes as the pH of the concrete exposedto acidifying conditions keeps dropping, resulting in the successivecascade of different microorganisms ecosystems that act upon theconcrete such that each pH zone and change is characterized by itsunique microorganism ecosystem.

SUMMARY OF THE INVENTION

The present invention relates to an additive formulation for reductionor prevention of microbially induced corrosion in concrete, in acementitious material (such as mortar or grout), or a combinationthereof.

In an embodiment of the invention, an additive formulation comprises:(1) a Quat Silane (QS) (also commonly referred to as a Silyl Quat or1-Octadecanaminium, N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-,chloride), preferably as an antibacterial additive to combatThiobacillus and other bacteria; (2) a fungicide, preferably to combatfusarium and other fungal species; and (3) an optional additive,preferably to offset side effects of QS in concrete. Non-limitingexamples of fungicides include, but are not limited to, SodiumOrthophenylPhenol (Microban P2); Imazalil Sulphate (Microban IF4);diiodomethyl-p-tolylsulfone; carbamates including, but not limited to,Iodopropynyl butylcarbamate (IPBC), carbendazim, and a combinationthereof; isothiazolinones including but not limited to, OIT(2-Octyl-2H-isothiazol-3-one), DCOIT(4,5-Dichloro-2-octyl-4-isothiazolin-3-one), BBIT (N-butyl-1,2-benzisothiazolin-3-one), and a combination thereof; azoles including,but not limited to, tebuconazole and propiconazole; chlorothalonil, zincpyrithione, copper pyrithione, sodium pyrithione, and a combinationthereof.

While the QS chemically bonds to silicates present in the final concretemixture, fungicides in concrete generally do not. Thus, the fungicidesmay be vulnerable to leaching by water. The degree of vulnerability is afunction of the water solubility of the fungicide, higher solubilityleads to higher leaching. One of the benefits of adding QS to a concretemixture is a large increase in the resistance of the concrete to theflow of water through its void spaces. Restricting this flow of wateralso inhibits the ability of the water to leach the fungicides (and anyother water-soluble chemicals) from the concrete, greatly reducing anymigration of the concrete. This will greatly increase the durability ofthe antifungal protection as well as reduce the release of thesechemicals into the sewage system.

The amount of the formulation in concrete may vary based on the severityof the environment and the desired level of protection. Totalformulation active levels between 75 ppm and 2500 ppm based on theweight of cement in the concrete (exclusive of the aggregate), forexample, will provide good protection based on the MIC levels measured.The ratio of the QS active to the selected fungicide(s) in theformulation is in a range of about 10:1 to about 1:10, preferably in arange of about 5:1 to about 1:5.

Other additives may be present such as a defoamer. The amount ofdefoamer is preferably from about 2 weight % to about 25 weight % of theamount of the QS in the formulation.

Adding antifungal efficacy to the concrete treatment for MICC is a noveland important addition to the mode of action of this formulation and issignificantly different than the products that are currently available.It was surprisingly found that pairing a fungicide with QS as anantibacterial active inhibits leaching and improves the durability ofany antifungal actives due in part to the hydrophobicity effect of theQS in concrete.

Further areas of applicability of the present invention will becomeapparent from the detailed description provided hereinafter. It shouldbe understood that the detailed description and specific examples, whileindicating the preferred embodiments of the invention, are intended forpurposes of illustration only and are not intended to limit the scope ofthe invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from thedetailed description and the accompanying drawings, which are notnecessarily to scale, wherein:

FIG. 1 is a graphical depiction of air entrainment versus QS dose levelillustrating that air entrainment rises as the level of QS increases.

FIG. 2 is a graphical depiction of set time versus QS dose levelillustrating that set time increases as the level of QS added increases.

FIG. 3 is a graphical depiction of strength versus QS dose levelillustrating that strength decreases as QS level increases.

FIG. 4 is a graphical depiction of percent water weight increase pertime illustrating results of water uptake testing on concrete samplesper ASTM C1585-13.

FIG. 5 is a graphical depiction of percent sample weight increase pertime illustrating results of water uptake testing on Ordinary PortlandCement (OPC) concrete samples treated with IF4 and/or a QS/defoamerformulation.

FIG. 6 is a graphical depiction of percent sample weight increase pertime illustrating results of water uptake testing on Ordinary PortlandCement (OPC) concrete samples treated with P2 and/or a QS/defoamerformulation.

FIG. 7 is a graphical depiction of percent sample weight increase pertime illustrating results of water uptake testing on 80% OrdinaryPortland Cement (OPC) and 20% (GGBS or slag) concrete samples treatedwith a range of QS/OIT formulations with (WD) and without (ND)incorporated defoamer.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following description of the embodiments of the present invention ismerely exemplary in nature and is in no way intended to limit theinvention, its application, or uses. The present invention has broadpotential application and utility. The following description is providedherein solely by way of example for purposes of providing an enablingdisclosure of the invention, but does not limit the scope or substanceof the invention.

As used herein, the terms “microbe” or “microbial” should be interpretedto refer to any of the microscopic organisms studied by microbiologistsor found in the use environment of a treated article. Such organismsinclude, but are not limited to, bacteria and fungi as well as othersingle-celled organisms such as mold, mildew and algae. Viral particlesand other infectious agents are also included in the term microbe.

“Antimicrobial” further should be understood to encompass bothmicrobicidal and microbistatic properties. That is, the term comprehendsmicrobe killing, leading to a reduction in number of microbes, as wellas a retarding effect of microbial growth, wherein numbers may remainmore or less constant (but nonetheless allowing for slightincrease/decrease).

For ease of discussion, this description uses the term antimicrobial todenote a broad spectrum activity (e.g. against bacteria and fungi). Whenspeaking of efficacy against a particular microorganism or taxonomicrank, the more focused term will be used (e.g. antifungal to denoteefficacy against fungal growth in particular).

Using the above example, it should be understood that efficacy againstfungi does not in any way preclude the possibility that the sameantimicrobial composition may demonstrate efficacy against another classof microbes.

For example, discussion of the strong antibacterial efficacydemonstrated by a disclosed embodiment should not be read to excludethat embodiment from also demonstrating antifungal activity. This methodof presentation should not be interpreted as limiting the scope of theinvention in any way.

The terms “concrete” and “cementitious material”, as used herein, areinterchangeable for purposes of the present invention.

Further, the term “or” as used in this disclosure and the appendedclaims is intended to mean an inclusive “or” rather than an exclusive“or.” That is, unless specified otherwise, or clear from the context,the phrase “X employs A or B” is intended to mean any of the naturalinclusive permutations. That is, the phrase “X employs A or B” issatisfied by any of the following instances: X employs A; X employs B;or X employs both A and B. In addition, the articles “a” and “an” asused in this application and the appended claims should generally beconstrued to mean “one or more” unless specified otherwise or clear fromthe context to be directed to a singular form. Throughout thespecification and claims, the following terms take at least the meaningsexplicitly associated herein, unless the context dictates otherwise. Themeanings identified below do not necessarily limit the terms, but merelyprovided illustrative examples for the terms. The meaning of “a,” “an,”and “the” may include plural references, and the meaning of “in” mayinclude “in” and “on.” The phrase “in one embodiment,” as used hereindoes not necessarily refer to the same embodiment, although it may.

The additive formulation of the present invention is useful to treatconcrete structures that are susceptible to microbially inducedcorrosion (MICC) (e.g. culverts, pipes, underground drains, manholesstructures, etc.) in order to slow or prevent MICC, extending the usefullife of such components. Replacing buried sewer components is extremelyexpensive, so extending the engineering life of the pipes and componentsis extremely important.

The additive formulation is to be formulated with fungicides as well asthe QS (which is mostly antibacterial), considerably broadening therange of protection that it offers. QS is extremely effective againstfungi in the wet state, but not as strong in the dry state. In addition,the additive formulation comprises ingredients that counteract anynegative side effects of QS on the concrete products.

In an embodiment of the invention, the additive formulation comprises:(1) QS, as an antibacterial additive to combat Thiobacillus and otherbacteria; (2) at least one additive to offset a side effect(s) of QS inconcrete; and (3) at least one fungicide to combat fusarium and otherfungal species. The ratio of QS to fungicide is in a range of about 10:1to about 1:10, preferably in a range of about 5:1 to about 1:5. Theseingredients are preferentially mixed in a non-aqueous or water-free,maximum concentration formulation to prevent QS hydrolysis and extendthe shelf life of the formulation, as well as to reduce the volume ofthe material that would be required to be shipped and stored at a majorworksite. A maximum concentration formulation can have, for example,active QS in a range of from about 3.6 weight % active to 72 weight %active. Alternatively, an RTU (Ready-To-Use) formulation can be preparedby dilution with water for ease of use on-site as long as shelf liferestrictions are observed to avoid degradation by hydrolysis. Theformulation of the present invention is dispersible in water.

Examples of an additive to offset a side effect(s) of QS in concreteinclude, but are not limited to, a defoamer, an accelerant (such ascalcium nitrate and/or sodium thiocyanate), a corrosion inhibitor (suchas calcium nitrite), an additive to reduce water permeability (such as acrystallization admixture), an additive to control slump/flowability(such as a superplasticizer), or a combination thereof. Non-limitingexamples of defoamers include, but are not limited to, polyether amine,ethoxylated alcohol, or silicone-based defoamers, tributyl phosphate, ora combination thereof.

Among the advantages of the formulation of the invention are thefollowing: It is a ready-to-use formulation that incorporates most orall ingredients in the appropriate proportions reduces the chance formixing errors in the field, and eases logistics on site as there are fewitems to track and store. An incorporated defoamer removes and/orreduces excess entrained air that negatively affects the performance ofthe concrete. Aqueous QS, during the wet state of the concrete, willeffectively reduce and kill bacteria and fungus so that the finishedconcrete object is created without entrained microbes. Cured QS in thefinal concrete object will provide good long term antibacterialprotection against organisms such as the Thiobacillus. It will alsoprovide increased hydrophobicity and increase the durability ofincorporated antifungal components by reducing leaching out of theconcrete. An incorporated fungicide will provide good long termprotection from fungal organisms such as Fusarium. The use of QS allowsthe effective employment of the additional antifungal component in adurable manner as the QS, in cured concrete, decreases waterpermeability and hence prevents a constantly active high pH environment(pH is operative when there is moisture) within the concrete and allowsemployment of fungicides that might otherwise be susceptible tohydrolytic instability due to the high pH and greatly reduces watergradients and capillary movement in the concrete and thus inhibits thefungicide from being leached out.

EXAMPLES Example 1

Table 1 indicates the MIC values generated against Th. novella, Fusariumand a combination of the two for two antifungal additives that weretested in the aqueous state.

TABLE 1 Active Ingredient Minimum Inhibitory Concentration ResultsStarkeya Fusarium Starkeya* + novella* oxysporum Fusarium Antifungal/QS(ppm) (ppm) (ppm) QS 7.8 15.6 31.3 P2 Untested 250 125 IF4 Untested 500500 *Starkeya novella and Thiobacillus novella are names for the sameorganism

The results in Table 1 indicated that in the aqueous state, the QS was astronger antifungal (lower concentration required for efficacy) than thetrialed antifungals.

In addition to testing the active ingredients alone, MIC tests wereconducted for combinations of the QS and the antifungal actives. An OITactive material was added to this test using the QS molecule tocompatibilize the mixture, making the mixture water soluble so MICtesting was possible. Table 2 summarizes the MIC data generated forthese actives:

TABLE 2 Active Combo Minimum Inhibitory Concentration Results StarkeyaFusarium Starkeya + novella oxysporum Fusarium Antifungal/QS (ppm) (ppm)(ppm) OIT:QS 1:1 7.8 15.6 15.6 1:2 7.8 15.6 15.6 2:1 7.8 15.6 15.6 P2:QS1:1 7.8 62.5 62.5 1:2 7.8 31.3 31.3 2:1 62.5 62.5 500 IF4:QS 1:1 3.931.3 62.5 1:2 3.9 31.3 31.3 2:1 31.3 62.5 62.5

Lower values indicated better performance. Compared to the charts of theMIC of the actives alone, it was apparent that the QS was providing theefficacy for the P2 and IF4 combinations—the antifungal (AF) additivewas simply diluting the QS so that more of the combination was requiredto get performance. However, a different dynamic was seen when lookingat the data for the OIT active, where the MIC values for the combo andthe QS alone are the same. This indicated that the OIT was performing aswell in the wet state as the QS for both the Th. novella, the Fusariumand the combination of the two. OIT may provide better dry filmantifungal performance while the QS may provide better dry filmantibacterial performance. Other possible antifungal actives that couldbe paired with the QS are carbamates such as Iodopropynyl butylcarbamate(IPBC) or carbendazim; isothiazolinones such as DCOIT or BBIT; azolessuch as tebuconazole or propiconazole; chlorothalonil,diiodomethyl-p-tolylsulfone, zinc pyrithione, copper pyrithione, sodiumpyrithione, or a combination thereof or any combination thereof.

For purposes of testing concrete, the following factors were considered.

-   -   Slump—A measure of consistency of concrete, related to        flowability and workability.    -   Entrained Air—Microscopic air cells in concrete relieve internal        pressure on the concrete by providing tiny chambers for water to        expand into when it freezes. This prevents freeze-thaw cracking.    -   Set Time—Initial set time is the time required for the concrete        to set sufficiently to resist penetration by a needle. Full cure        was 28 days (for testing).    -   Strength—The compressive strength of the concrete (in psi).

The addition of QS to concrete batches was observed to have surprisingand significant effects. First, the pseudo-surfactant nature of the QSmolecule caused a foaming action that resulted in the concreteentraining more air than was called for by design as shown in FIG. 1 .FIG. 1 is a graphical depiction of air entrainment versus QS dose levelillustrating that air entrainment rises as the level of QS increases.The dose level (gal/yd) is measured as the gallons per cubic yard of a3.6% active QS in water. Secondly, the curing reaction was retarded,resulting in longer cure times for the concrete as seen in FIG. 2 . FIG.2 is a graphical depiction of set time versus QS dose level illustratingthat set time increases as the level of QS added increases. The doselevel (gal/yd) is measured as the gallons per cubic yard of a 3.6%active QS in water. Strength measurements showed a decrease in 28-daycompressive strength as a function of the amount of QS added (FIG. 3 ).FIG. 3 is a graphical depiction of strength versus QS dose levelillustrating that strength decreases as QS level increases. The doselevel (gal/yd) is measured as the gallons per cubic yard of a 3.6%active QS in water. It was determined the increase in entrained air wasreducing strength, and controlling the entrained air removed any issueswith the final strength of the material. Once these issues were properlyidentified, additives to control the entrained air and to accelerate thecuring reaction were incorporated into the system to result in aconcrete product with no measurable physical performance differencesbetween treated and untreated (reference) samples.

TABLE 3 28 day Water/ Unit Set Compressive Concrete Slump WeightEntrained Time Strength Samples Ratio (inches) (lb/ft³) Air % Air %(min) (psi) Reference 0.514 3.5 147 3.2 3.50 540 6870 QS-5 0.493 4.5146.2 3.5 3.50 545 7070 3 gal/yd³ TB: 1 oz. NC: 80 oz/yd³

Table 3 lists the properties of QS-treated and untreated concretesamples with the amounts of tributyl phosphate defoamer (TB) and calciumnitrate accelerants (NC) incorporated into the system.

Negating the side effects of the QS on the concrete was importantbecause it allowed for higher treatment levels. The water permeabilityof treated concrete was shown to decrease as the letdown of QS wasincreased, as shown in FIG. 4 . FIG. 4 is a graphical depiction ofpercent water weight increase per time illustrating results of wateruptake testing on concrete samples per ASTM C1585-13. The abbreviationgal/yd is gallons per cubic yard of the 3.6% active QS additive. Theclear trend demonstrated that the treated samples showed about a 20%decrease in the amount of water absorbed over the length of the test (7days). The samples tested were at 0, 1, 3 and 5 gallons per cubic yardof a 3.6% active aqueous QS formulation.

Example 2—Leachability of Fungal Additives

The leachability of antifungal additives was tested. A matrix of OPCconcrete formulations was made using two water soluble antifungaladditives P2 (Na OPP) and IF4 (Amazalil Sulfate), added to concretemortar formulations with and without the QS additive as follows:

-   -   OPC with no additives    -   OPC with 5000 ppm IF4    -   OPC with 5000 ppm and 3 gal/cubic yd of QS with defoamer    -   OPC with 5000 ppm P2    -   OPC with 5000 ppm P2 and 3 gal/cubic yd of QS with defoamer

It was noted that 3 gal/cubic yd of the QS formulation corresponds to1500 ppm of QS active by weight of the cement binder, with Tributylphosphate (defoamer) mixed with the QS at 5% of the QS active level.Sample pucks were molded, cured and prepared for a water uptake test bydrying in a 70° C. oven until weight loss had ceased. The pucks werethen immersed into 30° C. water with their weight measured periodicallyto determine water uptake.

FIG. 5 is a graphical depiction of percent sample weight increase pertime illustrating results of water uptake testing on Ordinary PortlandCement (OPC) concrete samples treated with IF4 and/or a QS/defoamerformulation. The dose level of the QS/defoamer (gal/yd) is measured asthe gallons per cubic yard of concrete of a 3.6% active QS in water. Thesample pucks were dried in a 70° C. oven until the weight was stable for24 h, then immersed into 30° C. water with their weight measuredperiodically to determine water uptake. Two puck samples were averagedper point. The result is expressed as a present weight gain to indicatewater pickup and penetration into the sample.

FIG. 6 is a graphical depiction of percent sample weight increase pertime illustrating results of water uptake testing on Ordinary PortlandCement (OPC) concrete samples treated with P2 and/or a QS/defoamerformulation. The dose level of the QS/defoamer (gal/yd) is measured asthe gallons per cubic yard of concrete of a 3.6% active QS in water. Thesample pucks were dried in a 70° C. oven until the weight was stable for24 h, then immersed into water with their weight measured periodicallyto determine water uptake. Two puck samples were averaged per point. Theresult is expressed as a present weight gain to indicate water pickupand penetration into the sample.

It can be seen in FIGS. 5 and 6 that the QS treated samples gained watermore slowly than the fungicide alone samples. It can also be seen thatthe final percent uptake for all samples are within one percent of thefinal uptake percentage of the untreated OPC sample, indicating littlechange in the internal void space of the samples and therefore littlechange in percent air entrainment, demonstrating the efficacy of theincorporated defoamer. Table 4 indicates results of leach testing thesamples, to determine how quickly the water-soluble additives willmigrate into the water:

TABLE 4 # Soaking Hours: 72 288 OPC 5000 ppm IF4 90.5 ppm 106.25 ppm OPC5000 ppm IF4 & 59.5 ppm 60 ppm QS w/defoamer OPC 5000 ppm P2 285 ppm 340ppm OPC 5000 ppm P2 & 135 ppm 200 ppm QS w/defoamer

The samples were soaked at 50° C. with a constant swishing agitation,with HPLC used to measure the concentration of the fungal additives inthe leachate. Under these harsh conditions the samples untreated by theQS formulation release the antifungal additive 1.5 to 2 times fasterthan the QS treated samples. This surprisingly indicates a considerablefungal efficacy durability advantage when QS is used in concretesystems.

Example 3

OIT was tested as an antifungal additive in conjunction with QS.Concrete samples were made and treated with formulations of 2:1 QS:OITand 1:1 QS:OIT, with and without tributyl phosphate defoamer, and weretested using the water take up test discussed herein. The results areset forth in FIG. 7 .

FIG. 7 is a graphical depiction of percent sample weight increase pertime illustrating results of water uptake testing on 80% OrdinaryPortland Cement (OPC) and 20% (GGBS or slag) concrete samples treatedwith a range of QS/OIT formulations with (WD) and without (ND)incorporated defoamer. The ratio in each formulation description was theratio of QS to OIT active. The dose level of the QS/defoamer (gal/yd)was measured as the gallons per cubic yard of concrete of a 3.6% totalactive QS/OIT formulation in water. The sample pucks were dried in a 70°C. oven until the weight was stable for 24 h, then immersed into 30° C.water with their weight measured periodically to determine water uptake.Two puck samples were averaged per point. The result was expressed as apresent weight gain to indicate water pickup and penetration into thesample.

It was clearly seen that the two samples with no defoamer absorb morewater than the other samples, while the sample with the highest level ofQS absorbs the least showing the impact of the defoamer. Most samplesclustered about the untreated control sample indicating that the formulawas correctly compensating for the foaming effects of the QS.

Testing was also conducted to determine whether the addition of thedefoamer or mixing the QS and OIT together would have any effect on themicrobial efficacy of these components. MIC testing against Aspergillusniger and Fusarium oxysporum showed there was no effect. Results areshown in Table 5:

TABLE 5 Tributyl Fusarium Aspergillus Phosphate oxysporum nigerAntifungal/QS Defoamer (ppm) (ppm) OIT:QS 1:1 No 6.3 12.5 2:1 No 12.512.5 1:1 Yes 6.3 6.3 2:1 Yes 12.5 12.5 QS only No 15.6 125 OIT No 6.36.3

It will therefore be readily understood by those persons skilled in theart that the present invention is susceptible of broad utility andapplication. Many embodiments and adaptations of the present inventionother than those herein described, as well as many variations,modifications and equivalent arrangements, will be apparent from orreasonably suggested by the present invention and the foregoingdescription thereof, without departing from the substance or scope ofthe present invention. Accordingly, while the present invention has beendescribed herein in detail in relation to its preferred embodiment, itis to be understood that this disclosure is only illustrative andexemplary of the present invention and is made merely for purposes ofproviding a full and enabling disclosure of the invention. The foregoingdisclosure is not intended or to be construed to limit the presentinvention or otherwise to exclude any such other embodiments,adaptations, variations, modifications and equivalent arrangements.

What is claimed is:
 1. A formulation comprising: a material that is in awet-state in which the material is an uncured concrete, an uncuredcementitious material, or a combination thereof, a Quat Silane thatcures on and/or within the material, a fungicide selected from the groupconsisting of Sodium OrthophenylPhenol, Imazalil Sulphate,diiodomethyl-p-tolylsulfone, carbamate, isothiazolinone, azole,chlorothalonil, zinc pyrithione, copper pyrithione, sodium pyrithione,and a combination thereof, a defoamer from about 2 weight % to about 25weight % of the amount of the Quat Silane in the formulation, whereinthe ratio of the Quat Silane to the fungicide in the formulation is in arange of about 10:1 to about 1:10.
 2. The formulation according to claim1, wherein the ratio of the Quat Silane to the fungicide in theformulation is in a range of about 5:1 to about 1:5.
 3. The formulationaccording to claim 1, wherein the defoamer is selected from the groupconsisting of polyether amine, ethoxylated alcohol, silicone-baseddefoamer, tributyl phosphate, and a combination thereof.
 4. Theformulation according to claim 1, wherein the carbamate is selected fromthe group consisting of Iodopropynyl butylcarbamate (IPBC), carbendazim,and a combination thereof.
 5. The formulation according to claim 1,wherein the isothiazolinone is selected from the group consisting of OIT(2-Octyl-2H-isothiazol-3-one), DCOIT(4,5-Dichloro-2-octyl-4-isothiazolin-3-one), BBIT (N-butyl-1,2-benzisothiazolin-3-one), and a combination thereof.
 6. The formulationaccording to claim 1, wherein the azole is selected from the groupconsisting of tebuconazole and propiconazole, and a combination thereof.7. The formulation according to claim 1, wherein the Quat Silane ispresent at an effective amount to reduce bacteria and fungus in thematerial prior to curing.
 8. The formulation according to claim 2,wherein the defoamer is selected from the group consisting of polyetheramine, ethoxylated alcohol, silicone-based defoamer, tributyl phosphate,and a combination thereof.
 9. The formulation according to claim 8,wherein the carbamate is selected from the group consisting ofIodopropynyl butylcarbamate (IPBC), carbendazim, and a combinationthereof.
 10. The formulation according to claim 9, wherein theisothiazolinone is selected from the group consisting of OIT(2-Octyl-2H-isothiazol-3-one), DCOIT(4,5-Dichloro-2-octyl-4-isothiazolin-3-one), BBIT (N-butyl-1,2-benzisothiazolin-3-one), and a combination thereof.
 11. Theformulation according to claim 10, wherein the azole is selected fromthe group consisting of tebuconazole and propiconazole, and acombination thereof.
 12. The formulation according to claim 11, whereinthe Quat Silane is present at an effective amount to reduce bacteria andfungus in the material prior to curing.
 13. The formulation according toclaim 3, wherein the carbamate is selected from the group consisting ofIodopropynyl butylcarbamate (IPBC), carbendazim, and a combinationthereof.
 14. The formulation according to claim 13, wherein theisothiazolinone is selected from the group consisting of OIT(2-Octyl-2H-isothiazol-3-one), DCOIT(4,5-Dichloro-2-octyl-4-isothiazolin-3-one), BBIT (N-butyl-1,2-benzisothiazolin-3-one), and a combination thereof.
 15. Theformulation according to claim 14, wherein the azole is selected fromthe group consisting of tebuconazole and propiconazole, and acombination thereof.
 16. The formulation according to claim 15, whereinthe Quat Silane is present at an effective amount to reduce bacteria andfungus in the material prior to curing.